WO1994012609A1 - Detergent compositions with calcium ions and polyhydroxy fatty acid amide nonionic/selected anionic/soap surfactant mixture - Google Patents

Abstract

Mixed nonionic/anionic surfactants which comprise polyhydroxy fatty acid amides and anionic surfactants of the α-sulfonated fatty acid esters, alkyl ethoxylated sulfate, alkyl ethoxylated carboxylate, alkyl sulfate or sulfated alkyl polyglycoside types are used in various cleaning functions. Thus, C10-C22 fatty acid N-alkyl glucamides are combined with such anionic surfactants, a soap and a source of calcium ions. The resulting mixtures exhibit exceptionally low interfacial tension, especially in the presence of calcium ions. Mixtures of such nonionic/anionic/soap/calcium systems surfactants with conventional ethoxylated alcohol surfactants provide excellent removal of cosmetic stains from fabrics.

Description

DETERGENT COMPOSITIONS WITH CALCIUM IONS AND POLYHYDROXY FATTY ACID AMIDE NONIONIC/SELECTED ANIONIC/SOAP SURFACTANT MIXTURE

FIELD OF THE INVENTION The present invention relates to fully-formulated detergent compositions containing a polyhydroxy fatty acid amide surfactant, a member of a specially selected class of anionic surfactants, together with a soap. The resulting compositions yield extremely low interfacial tensions in aqueous media, especially in the presence of calcium ions, and are thus useful for cleaning operations.

BACKGROUND OF THE INVENTION Most conventional detergent compositions contain mixtures of various detersive surfactants in order to remove a wide variety of soils and stains from surfaces. For example, various anionic surfactants, especially the alkyl benzene sulfonates, are useful for removing particulate soils, and various nonionic surfactants, such as the alkyl ethoxylates and alkylphenol ethoxylates are useful for removing greasy soils. Accordingly, mixtures of anionic and nonionic surfactants are used in many modern detergent compositions.

While a review of the literature would seem to suggest that a wide selection of surfactants is available to the detergent manufacturer, the reality is that many such materials are specialty chemicals which are not suitable for routine use in low unit cost items such as home laundering compositions. The fact remains that most home-use detergents still comprise one or more of the conventional ethoxylated nonionic and sulfated or sulfon- ated anionic surfactants, presumably due to the economic and performance considerations noted below.

Unfortunately, many modern detersive surfactants are availa¬ ble mainly from nonrenewable resources, such as petrochemicals. Soaps, i.e., the salts of fatty acids, comprise traditional and time-honored class of surface-active agents. Soaps have the advantage that they are available via the hydrolysis of renewable resources such as plant and animal oils and fats. Unfortunately, soaps are quite susceptible to the formation of "curd" in the presence of water hardness. Moreover, soaps are not as effective for lowering solution interfacial tensions across conditions of pH and water hardness as are their counterpart synthetic surfactants, and are less effective cleaners, especially for grease and oil deposits.

Considerable attention has lately been directed to nonionic surfactants which can be prepared using mainly renewable resources, such as fatty acid esters and sugars. One such class of surfactants includes the pol hydroxy fatty acid amides.

Moreover, the combination of such nonionic surfactants with conventional anionic surfactants such as the alkyl sulfates, alkyl benzene sulfonates, alkyl ether sulfates, and the like, has also been studied. Attention is now being given to the improvement of such combinations of nonionic/anionic surfactants, especially with regard to their ability to reduce interfacial tensions and to provide improved grease/oil removal from a variety of substances. To achieve this goal, especially in the absence of phosphate builders, is a substantial challenge to the detergent formulator.

BACKGROUND ART A method for preparing crude polyhydroxy fatty acid amides (glucamides) is described in U.S. Patent 1,985,424, Piggott, and in U.S. Patent 2,703,798, Schwartz. The use of such glucamides with various synthetic anionic surfactants is described in U.S. Patent 2,965,576, corresponding to G.B. Patent 809,060. The sulfuric esters of acylated glucamines are disclosed in U.S. Patent 2,717,894, Schwartz. SUMMARY OF THE INVENTION

The present invention encompasses detergent compositions which provide an extremely low interfacial tension, comprising a mixed nonionic/anionic/soap surfactant system which comprises: (a) a polyhydroxy fatty acid amide of the formula 0 Rl

R2 - C - N - Z wherein Rl is H, C1-C3 hydrocarbyl, 2-hydroxyethyl ,

2-hydroxypropyl , or a mixture therein, R2 is C5-C32 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least two (in the case of glyceraldehyde), preferably at least three (in the case of other reducing sugars) hydroxyls directly connected to the chain; (b) an anionic surfactant which is a member selected from the group consisting of alpha-sulfonated fatty acid esters (also known as alkyl ester sulfonates), especially methyl esters ("MES"), alkyl alkoxylated sulfates, especially alkyl ethoxylated sulfates ("AES"), alkyl ethoxylated carboxylates ("AEC"), alkyl and alkenyl sulfates ("AS"), and sulfated alkyl polyglucosides ("SAP"); at a weight ratio of (a):(b) of from about 10:1 to about 1:10; (c) a soap; and

(d) a source of calcium ions.

The "anionic surfactants" employed herein are all well-known to detergent formulators. The C12-I8 alpha-sulfonated fatty acid methyl esters, the C12-I8 alkyl ethoxylated (E01-7, preferably 3) sulfates, the C12-I8 alkyl ethoxylated (E0 1-7, preferably 3-4) carboxylates, the C12-I8 primary and secondary alkyl and alkenyl (e.g., oleyl) sulfates and the sulfated C12-I8 alkyl polyglyco- sides are all fully described in the extensive patent and general literature on surfactants. The term "soaps" herein is intended to encompass the classic, conventional water-soluble salts of C o-Cis linear saturated and unsaturated fatty acids. Compositions according to the present invention containing such soaps exhibit quite low interfacial tensions and good grease removal properties, even at pH's near neutrality, i.e., in the range of ca. 6.5-11.0, and are thus quite useful for fabric laundering. As a general proposition, the improved qualities of the compositions herein appear to peak with soaps of about Cj2. and to decrease somewhat with soaps which are longer than about C13 and shorter than about Cπ, especially with respect to spontaneous e ulsification of greasy soils. Accord¬ ingly, the C12 soaps are preferred herein. The "soaps" can be employed in any water-soluble salt form, e.g., alkali metal, alkaline earth metals, ammonium, alkanolammonium, di- or tri- alkanolammonium, C1-.5 alkyl ammonium, basic amino acid groups, and the like, all of which are well-known to manufacturers. The sodium salt form is convenient, cheap and effective. The fatty acid form can also be used, but will usually be converted into the ionic form by pH adjustments which are made during processing of the compositions. Since water-soluble soaps are generally easier to work with, it is preferred that they be used, rather than the fatty acid form.

Nonlimiting examples of soaps useful herein include: deca- noate; undecanoate; laurate; undecyleneate; tridecanoate; 2-dodecenoate; and mixtures thereof.

The soaps typically comprise at least about 1% by weight of the compositions herein and preferably comprise from about 4% to about 10% by weight of the total compositions herein. Stated otherwise, the weight ratio of soap (c) to the combined mixture nonionic/anionic (a + b) is in the range c:(a + b) from about 1:20 to about 1:2, preferably about 1:9 to about 1:3.

Preferred compositions herein contain at least about 10%, preferably from about 25% to about 65%, by weight of said mixed nonionic/anionic/soap surfactant system. Such compositions typically comprise from about 5% to about 50% of the nonionic surfactant and from about 5% to about 50% of the anionic surfact¬ ant. Highly preferred are compositions which additionally contain from about 2% to about 40% by weight of an additional detersive surfactant, as well as other optional detersive adjuncts as disclosed hereinafter. Alkoxylated alcohols or alkoxylated alkyl phenols at levels of at least about 1%, preferably about 2% to about 6%, are especially preferred.

The invention thus encompasses compositions which comprise from about 10% to about 65% by weight of said mixed nonionic/ani¬ onic/soap surfactant system, from about 1% to about 15% by weight of an ethoxylated C8-C24 alcohol, and optional builders and detersive enzymes. Such compositions exhibit especially good removal of cosmetic stains from fabrics. The compositions herein will also contain from about 0.5% to about 2%, preferably from about 1% to about 1.5%, by weight, of calcium ions. High sudsing compositions will also contain from about 0.5% to about 2%, preferably about 1%, by weight of magnesium ions. Sources of calcium and magnesium can be any convenient water-soluble and toxicologically acceptable salt, including but not limited to, calcium formate, CaCl2» MgCl2_> Ca(0H)2, Mg(0H)2, CaBr2, MgBr2, Ca jnalate, Mg malate; Ca maleate, Mg maleate, or the calcium and/or magnesium salts of anionic surfactants or hydrotropes. C Cl2 and MgCl2 are convenient and preferred herein.

If builders are used in the compositions, it is preferred that they be non-phosphate builders such as citrate, zeolite or layered silicate. This allows a residuum of calcium ions to advantageously co-act with the surfactant system to help lower interfacial tension.

The invention also encompasses a method for reducing the interfacial tension (IFT; oil/water interface) in a system comprising water (e.g., a washing liquor) and oil (e.g., a stain or soil on solid surfaces, fabrics, dishware, and the. like) to a level of about 0.15 dynes/cm at the oil/water interface, whereby spontaneous emulsification can occur, thereby cleansing said solid surface. In general, usage levels of at least about 200 ppm, typically from about 300 ppm to about 3,000 ppm, of the composi¬ tions of this invention in water achieve this desirable result.

The invention also encompasses an improved method for removing greasy stains such as cosmetic stains from fabrics, comprising contacting the fabrics thus stained with an aqueous bath containing at least about 0.02% by weight of a composition which comprises said mixed nonionic/anionic surfactant system and said C8-C24 alkoxylated (preferably ethoxylated) alcohol or alkoxylated C8-C24 alkyl phenol (preferably ethoxylated).

All percentages, ratios and proportions herein are by weight, unless otherwise specified. All documents cited are incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

While the polyhydroxy fatty acid amides used herein can be prepared, for example, by the methods disclosed in the Schwartz references above, this invention most preferably employs high quality polyhydroxy fatty acid amide surfactants which are substantially free of cyclized by-products.

As an overall proposition, the preparative methods described in W0-9,206,154 and W0-9,206,984 will afford high quality poly- hydroxy fatty acid amides. The methods comprise reacting N-alkylamino polyols with, preferably, fatty acid methyl esters in a solvent using an alkoxide catalyst at temperatures of about 85^*C to provide high yields (90-98%) of polyhydroxy fatty acid amides having desirable low levels (typically, less than about 1.0%) of sub-optimally degradable cyclized by-products and also with improved color and improved color stability, e.g., Gardner Colors below about 4, preferably between 0 and 2. For high sudsing compositions, the N-methyl and N-hydroxyalkyl amine compounds are preferred. For low sudsers, the C2-C3 alkyl, preferably the N-C3 alkyl amine compounds, are used. (With some of the low sudsers, the methanol introduced via the catalyst or generated during the reaction provides sufficient fluidization that the use of additional reaction solvent may be optional.) If desired, any unreacted N-alkylamino polyol remaining in the product can be acylated with an acid anhydride, e.g., acetic anhydride, maleic anhydride, or the like, to minimize the overall level of amines in the product. By "cyclized by-products" herein is meant the undesirable reaction by-products of the primary reaction wherein it appears that the multiple hydroxyl groups in the polyhydroxy fatty acid amides can form ring structures which may not be readily biodegradable. It will be appreciated by those skilled in the chemical arts that the preparation of the polyhydroxy fatty acid amides herein using the di- and higher saccharides such as maltose will result in the formation of polyhydroxy fatty acid amides wherein linear substituent Z (which contains multiple hydroxy substituents) is naturally "capped" by a polyhydroxy ring structure. Such materials are not cyclized by-products, as defined herein.

More generally, the processes and compositions herein employ polyhydroxy fatty acid amide surfactants of the formula:

wherein: Rl is H, C1-C3 hydrocarbyl (C1-C2 is preferred for dishwashing; C3 is preferred for fabric laundering), 2-hydroxy- ethyl, 2-hydroxypropyl , or a mixture thereof, preferably C1-C4 alkyl, more preferably Ci or C2 alkyl, most preferably Cj alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl moiety, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain Cn-Cig alkyl or alkenyl, or mixture thereof; and Z is a poly- hydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can -be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be under¬ stood that it is by no means intended to exclude other suitable raw materials. Z preferably will be selected from the group consisting of -CH2-(CH0H)_n-CH20H, -CH(CH2θH)-(CHOH)_n-i-CH2θH, -CH2-(CHOH)2(CHOR')(CHOH)-CH2θH, where n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2θH.

In Formula (I), R¹ can be, for example, N-methyl, N-ethyl, N-propyl and N-2-hydroxy ethyl.

R2-C0-N< can be, for example, coca ide, stearamide, oleamide, laura ide, myristamide, capricamide, palmita ide, tallowamide, etc.

Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxyxylityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxyman- nityl, 1-deoxymaltotriotityl, 2,3-dihydroxypropyl (from glyceral¬ dehyde), etc. It will be appreciated that the polyhydroxy fatty acid amide surfactants used herein as the nonionic surfactant component can be mixtures of materials having various substituents R¹ and R².

Various "detersive adjunct" materials will preferably be used in fully-formulated detergent compositions containing the surfact- ant/soap/calcium mixtures of the present invention. The following are intended only to be nonlimiting Illustrations of such adjuncts, more examples of which will readily come to mind of the skilled formulator. Enzymes - Detersive enzymes can optionally be included in the detergent formulations for a wide variety of purposes, especially for fabric laundering, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and prevention of refugee dye transfer. The enzymes to be incorpor¬ ated include proteases, amylases, Upases, cellulases, and per- oxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases. Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.05 mg to about 3 mg, of active enzyme per gram of the composition.

Suitable examples of proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradena es ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands). Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).

Amylases include, for example, α-amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.

The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-0S-2.247.832.

Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also Upases in Japanese Patent Application 53-20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P." Other commercial Upases Include Amano-CES, Upases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum Upases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and Upases ex Pseudomonas gladioli .

Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application W089/099813, published October 19, 1989, by 0. Kirk, assigned to Novo Industries A/S.

A wide range of enzyme materials and means for their incorp¬ oration into synthetic detergent granules is also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al (). Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formula¬ tions, are disclosed in U.S. Patent 4,261,868, Hora et al, issued April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent 4,261,868, issued April 14, 1981 to Horn, et al, U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patents 4,261,868, 3,600,319, and 3,519,570.

In addition to enzymes, the compositions herein xan option¬ ally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, color¬ ants, dyes, etc.).

Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness.

Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.

The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Liquid formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.

Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphos- phates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric eta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbon- ates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales. Importantly, the composi¬ tions herein function surprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders.

Examples of silicate builders are the alkali metal silicates, particularly those having a Siθ2: a2θ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. However, other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems. .

Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973. Aluminosilicate builders are especially useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent composi¬ tions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:

M_z(zAlθ2-ySiθ2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2; and y is 1; this material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaC03 hardness per gram of anhydrous aluminosili¬ cate. Preferred aluminosilicates are zeolite builders which have the formula:

Na₂[(Alθ2)_z (Siθ2) ]-xH2θ wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.

Useful aluminosilicate ion exchange materials are commer¬ cially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosili- cates or synthetically derived. A method for producing alumino¬ silicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X. In an especially preferred embodi¬ ment, the crystalline aluminosilicate ion exchange material has the formula:

Nai2[(Alθ2)l2(Siθ2)i₂]-xH2θ wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycar- boxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of poly¬ carboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.

Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S.

Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the ether hydroxy- polycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisul- phonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricar- boxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof. Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular composi¬ tions, especially in combination with zeolite and/or layered silicate builders.

Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuc- cinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccin- ates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986. Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 3,723,322.

In situations where phosphorus builders can be used, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphates and sodium orthophosphates can be used. Phosphate builders such as ethane-1- hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,090; 3,442,021; 3,400,148; and 3,422,137) can also be used.

Bleaching Compounds - Bleaching Agents and Bleach Activators - The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When present, bleaching agents will typically be at levels of from about 1% to about 20%, more typically from about 1% to about 10%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.

The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein, but, under some conditions, may undesirably interact with the polyol nonionic surfactant.

One category of bleaching agent that can be used without restriction encompasses percarboxylic ("percarbonate") acid bleaching agents and salts therein. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4- oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354,

Banks et al, published February 20, 1985, and U.S. Patent

4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al .

Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxy- hydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., 0X0NE, manufactured commercially by DuPont) can also be used.

Mixtures of bleaching agents can also be used.

Peroxygen bleaching agents and the perborates are preferably combined with bleach activators, which lead to the in situ produc¬ tion in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator. Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non- oxygen bleaching agent of particular interest includes photo- activated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holco be et al. Typically, detergent compositions will contain about 0.025% to about 1.25%, by weight, of sulfonated zinc phthalocyanine.

Polymeric Soil Release Agent - Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.

The polymeric soil release agents for which performance is enhanced herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxy- propylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3 oxyalkyl- ene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C3 oxyalkylene terephthalate units is about 2:1 or lower, (ii) C4-C6 alkylene or oxy C4-C6 alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably poly(vinyl acetate), having a degree of polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl ether substitu- ents, or mixtures therein, wherein said substituents -are present in the form of C1-C4 alkyl ether or C4 hydroxyalkyl ether cellu¬ lose derivatives, or mixtures therein, and such cellulose deriva¬ tives are amphiphilic, whereby they have a sufficient level of C1-C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon conventional polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls, once adhered to such conventional synthetic fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and (b). Typically, the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from 2 to about 200, although higher levels can be used, preferably from 3 to about 150-, more prefer¬ ably from 6 to about 100. Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as Mθ3S(CH2)nOCH2CH2θ-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.

Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellu- losic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al . Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Ci-Cβ vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).

One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975. Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.

Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J. J. Scheibel and E. P. Gosselink.

Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.

Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfo- aroyl, end-capped terephthalate esters.

If utilized, soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent composi- tions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.

Chelatino Agents - The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydrox eth lethylenedi- aminetriacetates, nitrilotriacetates, ethylenediamine tetrapropri- onates, triethylenetetraaminehexaacetates, diethylenetriamine- pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephos- phonates), nitrilotris (methylenephosphonates) and diethylenetri- aminepentakis (methylenephosphonates). Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al . Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethyl- enediamine disuccinate ("EDDS"), as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins. If utilized, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent composi¬ tions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.

Clay Soil Removal/Anti-redeoosition Agents - The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; liquixi detergent compositions typically contain about 0.01% to about 5%.

The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil removal/antiredeposition agents are the cationic compounds dis¬ closed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. Another type of preferred anti- redeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art. Polymeric Dispersing Agents - Polymeric dispersing agents can advantageously be utilized at levels from about 0.1% to about 7%, by weight, in the compositions herein. These materials can also aid in calcium and magnesium hardness control. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated onomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982.

Another polymeric material which can be included is poly¬ ethylene glycol (PEG). PEG can exhibit dispersing agent perform- ance as well as act as a clay soil removal/antiredeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.

Briohtener - Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent compositions herein. Commercial optical brighteners which may be useful in the present invention can be classified into subgroups which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).

Specific examples of optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba- Geigy; Arctic White CC and Artie White CWD, available from Hilton- Davis, located in Italy; the 2-(4-styryl-phenyl)-2H- naphthol[l,2- d]triazoles; 4,4'-bis- (l,2,3-triazol-2-yl)-stil- benes; 4,4'-bis- (styryl)bisphenyls; and the y-aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl- amino coumarin; l,2-bis(-benzimidazol-2-yl)ethylene; 1,3-diphenylphrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naphth-[l,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [l,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. The incorporation of such materials, herein¬ after "suds suppressors," in laundry or hard surface cleaning applications, can be desirable to further reduce the sudsing of the mixed nonionic/anionic surfactants herein. Additional suds suppression can be of particular importance when the detergent compositions herein optionally include a relatively high sudsing surfactant in combination with the low-sudsing mixed nonionic/ani- onic surfactants of this invention.

A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of particular interest encompasses monocarboxylic fatty acids and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

The detergent compositions herein may also contain non- surfactant suds suppressors. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g. stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g. K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40^*C and about 5^*C, and a minimum boiling point not less than about 110^*C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferrably having a melting point below about 100^*C. The hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocar- bon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al . The hydrocar¬ bons, thus, include aliphatic, alicyclic, aromatic, and hetero- cyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant suds comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combina¬ tions of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed of fused onto the silica. Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.

Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relates to compositions and processes for defoam- ing aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.

Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.

An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of: (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1500 cs. at 25^*C; (ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3 Si0ι/2 units of Siθ2 units in a ratio of from (CH3)3 SiOj/2 units and to S1O2 units of from about 0.6:1 to about 1.2:1; and (iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel; In the preferred silicone suds suppressor used herein, the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), and not polypropylene glycol. The primary silicone suds suppressor is branched/crosslinked and not linear.

To illustrate this point further, typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from abut 0.05 to about 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471, Starch, issued December 18, 1990, and 4,983,316, Starch, issued January 8, 1991, and U.S. Patents 4,639,489 and 4,749.740, Aizawa et al at column 1, line 46 through column 4, line 35. The silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/poly- propylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.

The preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol .

The preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLUR0NIC L101.

Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C6-Ci6 alkyl alcohols having a C1-C16 chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark IS0F0L 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 5:1.

For any detergent compositions to be used in automatic laundry washing machines, suds should not form to the extent that they overflow the washing machine. Suds suppressors, when utilized, are preferably present in a "suds suppressing amount." By "suds suppressing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.

The low-sudsing compositions herein will generally comprise from 0% to about 5% of suds suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to about 5%, by weight, of the detergent composition. Preferably, from about 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized. Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarly to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%. As used herein, these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used.

In addition to the foregoing ingredients which are generally employed in fabric laundry, dishwashing and hard surface cleaners for cleansing and sanitizing purposes, the surfactant compositions herein can also be used with a variety of other adjunct ingredi- ents which provide still other benefits in various compositions within the scope of this invention. The following illustrates a variety of such adjunct ingredients, but is not intended to be limiting therein.

Fabric Softeners - Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can be used typically at levels of from about 0.5% to about 10% by weight in the present composi¬ tions to provide fabric softener benefits concurrently with fabric cleaning. The polyhydroxy fatty acid amides of the present invention cause less interference with the softening performance of the clay than do the common polyethylene oxide nonionic sur¬ factants of the art. Clay softeners can be used in combination with amine and cationic softeners, as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, 1981.

Hair Care Ingredients - Shampoo compositions formulated in the manner of this invention can contain from about 0.05% to about 10% by weight of various agents such as: conditioners, e.g., silicones (see, for example, U.S. Patents 4,152,416 and 4,364,847); antidandruff agents such as the pyridinethiones, especially zinc pyridinethione (see U.S. Patents 4,379,753 and 4,345,080), selenium compounds such as selenium sulfide and OCTOPIROX; hair styling polymers (see U.S. Patents 4,012,501 and 4,272,511); and pediculicides (anti-lice agents) such as LINDANE and various pyrethrins (see British Patent 1,593,601 and U.S. Patent 4,668,666). Other Ingredients - A wide variety of other ingredients useful in detergent compositions can be included in the composi¬ tions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, etc. Various detersive ingredients employed in the present compo¬ sitions advantageously can be stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.

To illustrate this technique in more detail, a porous hydro¬ phobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of Cχ3_i5 ethoxylated alcohol E0(7) nonionic surfactant. Typically, the enzyme/surfact¬ ant solution is 2.5 X the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used). The result- ing silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in deter- gents, including liquid laundry detergent compositions.

Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2- propanediol) can also be used. Formulations - The formulation of effective, modern detergent compositions poses a considerable challenge, especially in the absence of phosphate builders. For fabric laundering, the formu¬ lator is required to address the removal of a wide variety of soils and stains, many of which are termed "greasy/oily" soils, such as foods, cosmetics, motor oil, and the like, from a wide variety of fabric surfaces and under a spectrum of usage condi¬ tions, ranging from boil wash temperatures preferred by some users to laundering temperatures as cold as 5*C preferred by others. Local factors, especially water hardness levels and the presence or absence of metal cations such as iron in local.wash water supplies, can dramatically impact detergency performance. Like¬ wise, the formulator of hand dishwashing compositions must provide compositions which remove high loads of greasy food residues, but which do so under conditions which are not irritating to the user's skin nor damaging to the articles being washed. It is especially difficult to provide good grease removal at near- neutral pH's.

It will be appreciated by the formulators of detergent compositions that, at sufficiently low interfacial tensions, it is theoretically possible to provide what might be termed "spontane¬ ous emulsification" of greasy/oily soil. If such spontaneous emulsification were to be secured, it would very considerably enhance grease/oil removal from substrates such as fabrics, dishware, environmental hard surfaces, and the like. While extremely low interfacial tensions and, presumably, spontaneous emulsification, have possibly been achievable with specialized surfactants such as the fluorinated surfactants known in the art, the present invention provides a new, mild surfactant system to achieve this desirable result. Moreover, spontaneous emulsifica¬ tion may be achievable with some specialized surfactants only at relatively high pH's in the range of 10-11, whereas this desirable result is also achievable with the present compositions even in the near-neutral pH range of about 6.5-8. This is particularly important for hand-washing operations, for example, hand dishwash¬ ing, where skin mildness is of concern to the user.

While the polyhydroxy fatty . acid amides employed in the practice of this invention are, structurally, nonionic-type surfactants and are referred to herein as "nonionics". It now also appears that the conformation of the polyhydroxy fatty acid amides may be changed due to interaction between water hardness ions, especially calcium cations, and the soap or anionic surfact- ant. This may increase the molecular packing of the polyhydroxy fatty acid amides at the air/water interface. Whatever the explanation at the molecular level, the net result is the lower interfacial tensions and improved cleaning benefits associated with the compositions of this invention, especially with respect to greasy/oily stains.

INTERFACIAL TENSION By "interfacial tension" ("IFT") herein is meant the tension measured at the oil/water interface. IFT measurements using the spinning drop technique, are disclosed by Cayias, Schechter and Wade, "The Measurement of Low Interfacial Tension via the Spinning Drop Technique", ACS Symposium Series No. 8 (1975) ADSORPTION AT INTERFACES, beginning at page 234. Equipment for running IFT measurements is currently available from W. H. Wade, Depts. of Chemistry and Chemical Engineering, The University of Texas at Austin, Austin, Texas 78712.

By "low interfacial tension" herein is meant an IFT which is sufficiently low that "spontaneous emulsification", i.e., rapid emulsification with little or no mechanical agitation, can occur. For example, using a typical fatty acid N-methyl glucamide nonionic surfactant, at concentrations in water ranging from about 300 ppm to about 600 ppm and at water hardness (Ca++) concentra¬ tions of 2 grains/gallon (14 ppm), 7 gr/gal (48 ppm) and 15 gr/gal (103 ppm) one notes a range of IFT from about 0.25 dynes/cm to about 0.4 dynes/cm. Under such conditions, "spontaneous emulsifi- cation" of grease/oil soil, if any, is minimal.

By contrast, when the aforesaid nonionic surfactant is employed with an anionic surfactant and a soap in the manner of this invention, especially in the presence of calcium ions, the IFT is reduced to 0.15 dynes/cm, or less, and spontaneous oil emulsification is noted.

SPONTANEOUS EMULSIFICATION The "spontaneous emulsification" of greasy/oily soils pro¬ vided by the compositions herein can be simply, but convincingly, demonstrated by admixing a detergent composition in accordance with the invention containing the specially selected soap with water. After dissolution of the detergent, a few drops of oil to which a colored oil-soluble dye has been added are added to the detergent solution. With minimal agitation, the entire system appears to take on the color of the dye, due to the dyed oil having been finely dispersed by the spontaneous emulsification effect. This dispersion remains for a considerable length of time, typically 30 minutes to several hours, even when agitation has stopped. By contrast, with surfactant systems which fail to provide spontaneous emulsification, the dyed oil droplets produced during agitation rapidly coalesce to form one or more relatively large oil globules at the air/water interface.

More specifically, this demonstration of spontaneous emulsi- fication can be run as follows.

A consumer relevant test soil is dyed with 0.5% Oil Red EGN. A 100 ml sample of the detergent composition being tested is prepared at the desired concentration (typically, about 500 ppm) and temperature in water which is "pre-hardened" to any desired concentration of calcium ions (typically, about 48 ppm), and contained in an 8 oz. capped jar. The sample pH is adjusted to the intended end-use pH (typically in the range of 6.5 to 8) and 0.2 g of the test soil is added. The jar is shaken 4 times and the sample graded. Alternatively, the sample is placed in a beaker and stirred with a stir bar for 15 seconds. The sample is graded as follows:

0 = Clear solution with large red oil droplets in it (0.1-5 mm diameter), i.e., no emulsification;

1 = Solution has a definite pink appearance with red oil droplets in it (0.1-1 mm), i.e., slight emulsification;

2 = Solution is dark pink with small red droplets in it, i.e., moderate emulsification;

3 = Solution is red with small red droplets in it (1-200/un), i.e., emulsification is substantial; 4 = Solution is dark red with little or no visible droplets

(<l-50μm), i.e., emulsification is complete. Note: The grading can also be done spectrophotometrically (based on light transmittance). It will further be appreciated that, while the calcium and/or optional magnesium ions may be incorporated into the compositions herein, the formulator may determine that it is acceptable prac¬ tice to rely on natural water hardness to provide such ions to the compositions under in-use situations. This may be a reasonable expedient, since as little as 2 gr/gal calcium hardness can provide substantial benefits. However, the formulator will most likely decide to add the calcium and/or optional magnesium ions directly to the compositions, thereby assuring their presence in the in-use situation. Under such circumstances, and especially when formulating liquid products wherein the presence -of precipi¬ tates may be undesirable, it is preferred to add the calcium and/or magnesium to the compositions in the form of a lightly co plexed chelate, such as calcium malate or maleate, magnesium malate or maleate, or the like.

The detergent compositions herein will preferably be formu¬ lated such that during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and about 10.5. Liquid product formulations preferably have a pH between about 7.5 and about 9.5, more preferably between about 7.5 and about 9.0. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art. The following are typical, nonlimiting examples which illus¬ trate the use of the mixed nonionic/anionic surfactant systems provided by this invention to prepare fully-formulated detergent compositions which can achieve the desired low IFT's and spontane¬ ous emulsification (grades 3-4) noted above. EXAMPLE I

A liquid detergent composition herein comprises the following.

Ingredient % fwt.)

Nonionic/anionic* 15.0 Sodium citrate 1.0

Cio alcohol ethoxylate (3) 13.0

Monoethanolamine 2.5

Ca maleate 1.0 Water/propylene glycol/ethanol (100:1:1) Balance

*1:1 mixture of coconutalkyl N-methyl glucamide: C12-C14 (E0)3 carboxylate.

EXAMPLE II A granular detergent herein comprises the following. Ingredient % (wt.)

Nonionic/anionic* 10.0

Zeolite A (1-10 micrometer) 30.0

Sodium citrate 10.0 Sodium carbonate 20.0

Optical brightener 0.1

Detersive enzyme** 1.0

C12-14 alkyl sulfate, Na 5.0

Sodium sulfate 15.0 CaCl2 1.2

Water and minors Balance

*1:1 mixture of tallowalkyl N-methyl glucamide and sulfated ClO-14 polyglucoside.

**Lipolytic enzyme preparation (LIPOLASE). EXAMPLE III

The compositions of Example I and II are modified by including 0.5% of a commercial proteolytic enzyme preparation (ESPERASE) therein. Optionally, 0.5% of a commercial a ylase preparation (TERMAMYL) and 0.5% of a commercial lipolytic enzyme preparation (LIPOLASE) can be co-incorporated in such liquid and solid detergent compositions.

EXAMPLE IV A dishwashing composition with high grease removal properties is as follows. Ingredient % (wt.)

Nonionic/anionic* 20.0

C12 sulfobetaine** 5.0

Ca maleate 1.0

Coconut monoethanolamine 1.0 Water Balance

*Cχ2-Ci4 fatty acid amide of N-methyl gluca ine or N-ethyl fructamine and secondary C12-I6 alkyl sulfate as a 3:1 nonionic:anionic mixture and neutralized partly with MgSθ4 and partly with NaOH to provide an overall Mg content in finished detergent compositions of 1.6%.

**Suds boosting surfactant aka "sultaine".

EXAMPLE V A shampoo composition is prepared according to Example IV by deleting the magnesium ions.

It has now been determined that the present compositions are especially useful for removing cosmetic stains from fabrics. This is an especially important technical improvement in detergency performance. Cosmetics, or facial "make-up", lipstick and the like, typically comprise a complex mixture of finely-ground, highly colored particulate material which is intimately admixed with a greasy or waxy carrier. Cosmetics are specifically formulated to remain on the surface to which they are applied, and for this reason their carriers are water-insoluble and/or water repellent. As is well-known, once a lipstick or other cosmetic smear is established on a fabric, its removal can prove extremely difficult. By comparison, the removal of cosmetic stains from fabrics is substantially more difficult than is the removal of common greasy stains such as lard. Compositions according to the present invention which additionally comprise from about 1% to about 20% by weight of an ethoxylated (EO 1-7; preferably 2-3) C12-C18 alcohol or alkyl phenol are preferably used in such formulations to further boost performance. The foregoing disclosure and Examples illustrate the practice of this invention in considerable detail. It is to be appreci¬ ated, however, that the advantages afforded by the compositions and processes of this invention are broadly useful with a variety of other technologies which have been developed for use in a wide variety of modern, fully-formulated cleaning compositions, espe¬ cially laundry detergents. The compositions herein will typically be used in aqueous media at concentrations of at least about 200 ppm, e.g., for lightly-soiled fabrics and/or hand dishwashing. Higher usage concentrations in the range of 1,000 ppm to 8,000 ppm, and higher, are used for heavily-soiled fabrics. However, usage levels can vary, depending on the desires of the user, soil loads, soil types, and the like. Wash temperatures can range from 5'C to the boil. It will be further appreciated that the invention encompasses a method for lowering IFT's of oil/grease (especially triglyceride fats and oils) in the presence of water, comprising admixing in said water at least about 200 ppm of the compositions herein. Such lowering of IFT also provides a means for achieving spontane¬ ous emulsification which is useful not only in fabric and hard surface cleaning, but also in any circumstance where it is import¬ ant to render oily materials more fluid, e.g., petroleum recovery and transmission, cosmetic formulations, and the like.

Claims

WHAT IS CLAIMED IS:

1. A detergent composition comprising a nonionic/anionic/soap surfactant system which comprises:

(a) a polyhydroxy fatty acid amide of the formula

0 R R2 - C - N - Z wherein Rl is H, C1-C3 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture therein, R² is C5-C32 hydrocarbyl, a Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least two hydroxyls directly connected to the chain; -

(b) an anionic surfactant which is a member selected from the group consisting of alpha-sulfonated fatty acids, alkyl alkoxylated sulfates, alkyl ethoxylated carboxylates, alkyl and alkenyl sulfates and sulfated alkyl polyglycosides, at a weight ratio of (a):(b) of from about 10:1 to about 1:10;

(c) a soap; and

(d) a source of calcium ions.

2. A composition according to Claim 1 which contains at least about 10% by weight of said nonionic/anionic/soap surfactant system.

3. A composition according to Claim 2 which additionally contains from about 2% to about 40% by weight of an additional detersive surfactant.

4. A composition according to Claim 3 wherein the additional surfactant comprises an alkoxylated alcohol or alkoxylated alkyl phenol .

5. A composition according to Claim 1 which comprises at least about 15% by weight of said mixed nonionic/anionic/soap surfactant system, at least about 1% by weight of an ethoxylated C8-C24 alcohol, and optional builders and detersive enzymes.

6. A method for lowering the interfacial tension of an oil/water system to 0.15 dynes/cm, or less, by dissolving in said system at least about 200 ppm of a composition according to Claim 1.